Zeolite SSZ-19

ABSTRACT

A crystalline silicaceous material, referred to as zeolite SSZ-19 or SSZ-19, having the characteristic X-ray diffraction lines of Table I is prepared with a reaction mixture containing an organic template component which can be a cycloalkyl trimethylammonium compound, a 1-azoniaspiroalkyl compound, a 1-azoniabicyclo [2.2.2] octane lower alkyl compound, or a 2,2-methyl lower alkyl trimethylammonium compound. The products are useful as catalysts and adsorbents.

BACKGROUND OF THE INVENTION

Natural and synthetic zeolite crystalline aluminosilicates are useful ascatalysts and adsorbents. These aluminosilicates have distinct crystalstructures which are demonstrated by X-ray diffraction. The crystalstructure defines cavities and pores which are characteristic of thedifferent species. The adsorptive and catalytic properties of eachcrystalline aluminosilicate are determined in part by the dimensions ofits pores and cavities. Thus, the utility of a particular zeolite in aparticular application depends at least partly on its crystal structure.

Because of their unique molecular sieving characteristics, as well astheir catalytic properties, crystalline aluminosilicates are especiallyuseful in such applications as gas drying and separation and hydrocarbonconversion. Although many different crystalline aluminosilicates andsilicates have been disclosed, there is a continuing need for newzeolites and silicates with desirable properties for gas separation anddrying, hydrocarbon and chemical conversions, and other applications.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth salts, silica, and alumina."Nitrogenous zeolites" have been prepared from reaction mixturescontaining an organic templating agent, usually a nitrogen-containingorganic cation. By varying the synthesis conditions and the compositionof the reaction mixture, different zeolites can be formed using the sametemplating agent. Use of N,N,N-trimethyl cyclopentylammonium iodide inthe preparation of Zeolite SSZ-15 molecular sieve is disclosed in mycopending application Ser. No. 437,709, filed on Oct. 29, 1982. Use of1-azoniaspiro [4.4] nonyl bromide and N,N,N-trimethyl neopentylammoniumiodide in the preparation of a molecular sieve termed "Losod" isdisclosed in Helv. Chim. Acta (1974); Vol. 57, page 1533 (W. Sieber andW. M. Meier). Use of quinuclidinium compounds to prepare a zeolitetermed "NU-3" is disclosed in European Patent Publication No. 40016. Useof 1,4-di(1-azoniabicyclo [2.2.2.]octane) lower alkyl compounds in thepreparation of Zeolite SSZ-16 molecular sieve is disclosed in mycopending application Ser. No. 425,786, filed on Sept. 28, 1982.

SUMMARY OF THE INVENTION

I have prepared a family of crystalline aluminosilicate molecular sieveswith unique properties, referred to herein as "Zeolite SSZ-19", orsimply "SSZ-19", and have found a highly effective method for preparingSSZ-19.

SSZ-19 has a mole ratio of an oxide selected from silicon oxide,germanium oxide, and mixtures thereof to an oxide selected from aluminumoxide, gallium oxide, and mixtures thereof greater than about 5:1 andhas the characteristic X-ray diffraction lines of Table 1. SSZ-19 has acomposition, as synthesized and in the anhydrous state, in terms of moleratios of oxides, as follows: (0.5 to 1.0)R₂ O:(0 to 0.50)M₂ O:W₂ O₃:(greater than 6)YO₂ wherein M is an alkali metal cation, W is selectedfrom aluminum, gallium, and mixtures thereof, Y is selected fromsilicon, germanium and mixtures thereof, and R is an organic cation.

One preferred form of SSZ-19 is a zeolitic crystalline aluminosilicatehaving a SiO₂ :Al₂ O₃ mole ratio greater than about 6:1. Theas-synthesized silica:alumina mole ratio is typically above about 10:1.The silica: alumina mole ratio of SSZ-19 can be increased by standardacid leaching or chelating techniques and by using silicon and carbonhalides and similar compounds. By use of such known methods for removingaluminum from the crystal structure, essentially aluminum-free forms ofSSZ-19 can be prepared. Preferably, for adsorption and drying uses,SSZ-19 is employed in the form of an aluminosilicate.

SSZ-19 crystals may be prepared by a highly efficient method comprisingforming an aqueous mixture containing sources of an organicnitrogen-containing compound as defined herein, an oxide selected fromaluminum oxide, gallium oxide, and mixtures thereof, and an oxideselected from silicon oxide, germanium oxide, and mixtures thereof, andhaving a composition, in terms of mole ratios of oxides, falling withinthe following ranges: YO₂ /W₂ O₃, above 6:1; R₂ O/W₂ O₃, 0.5:1 to 40:1;and OH⁻ /YO₂, greater than about 0.80:1; wherein Y is selected fromsilicon, germanium, and mixtures thereof, W is selected from aluminum,gallium and mixtures thereof, and R is an organic cation; maintainingthe mixture at a temperature of at least 110° C. until the crystals ofSSZ-19 are formed; and recovering said crystals. My method for preparingSSZ-19 is notable in using a combination of relatively high hydroxidecontents and relatively high SiO₂ /Al₂ O₃ ratios in the reactionmixture.

DETAILED DESCRIPTION OF THE INVENTION

SSZ-19 possesses a crystalline structure having an X-ray powderdiffraction pattern with the characteristic lines as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                              Relative                                                2 θ      d/n    Intensity                                               ______________________________________                                        7.88           11.22  22                                                      11.72          7.55   50                                                      13.64          6.49   40                                                      15.84          5.59   13                                                      18.00          4.93   70                                                      19.20          4.62   40                                                      20.90          4.25   12                                                      22.68          3.92   100                                                     23.75          3.75   56                                                      27.40          3.25   70                                                      30.00          2.98   16                                                      30.70          2.91   22                                                      ______________________________________                                    

Typical specific SSZ-19 aluminosilicate preparations, as synthesized,have the X-ray diffraction patterns of Tables 2, 3 and 5.

The X-ray powder diffraction patterns shown in the Tables weredetermined by standard techniques. The radiation was the K-alpha/doubletof copper. A scintillation counter spectrometer with a strip-chart penrecorder was used. The peak heights I and the positions, as a functionof 2 θ where θ is the Bragg angle, were read from the spectrometerchart. From these measured values, the relative intensities, 100I/I₀(where I₀ is the intensity of the strongest line or peak, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines)can be calculated.

SSZ-19, as synthesized, and as modified by exchanging the originalSSZ-19 cations with various other cations or removing aluminum from thecrystalline lattice, yields substantially the same diffraction pattern.There can be minor shifts in interplanar spacing and minor variations inrelative intensity due to one or more of such variables as (1) templatecompound employed, (2) silica:alumina mole ratio, and (3) calciningtechnique. Notwithstanding such minor variations, the diffractionpattern of the basic crystal lattice structure remains essentially thesame.

SSZ-19 crystals can be suitably prepared from an aqueous solutioncontaining sources of an alkali metal oxide, an organic compound of thetype specified herein, an oxide of aluminum or gallium, or mixture ofthe two, and an oxide of silicon or germanium, or mixture of the two.The reaction mixture should have a composition in terms of mole ratiosof oxides falling within the following ranges:

    ______________________________________                                                      Broad Preferred                                                 ______________________________________                                        YO.sub.2 /W.sub.2 O.sub.3                                                                     >6      >15                                                   M.sub.2 O/W.sub.2 O.sub.3                                                                      1-50   10-30                                                 R.sub.2 O/W.sub.2 O.sub.3                                                                     0.5-40   5-25                                                 OH.sup.- /YO.sub.2                                                                            >0.80   0.95-1.1                                              ______________________________________                                    

where R is an organic cation derived from a compound of the typespecified herein, Y is silicon, germanium or both, and W is aluminum,gallium or both. M is an alkali metal, preferably sodium. The organiccompound employed can provide hydroxide ion.

"Essentially alumina-free", as used herein with reference to acrystalline silica polymorph having the SSZ-19 crystal structure (anessentially alumina-free, silicaceous, crystalline molecular sieve),means a material having a silica:alumina mole ratio of greater than200:1, preferably greater than 500:1, and more preferably greater than1000:1.

The organic template component added to the reaction mixture used forcrystallization can be a cycloalkyl trimethyl heteroatom compound. Theheteroatom can be nitrogen or phosphorus. The preferred organic speciesare compounds which are sources of cyclohexyl trimethylammonium cationsor cyclopentyl trimethylammonium cations. The cyclopentyltrimethylammonium cation sources are especially preferred compounds foruse in preparing the reaction mixture.

The organic templating component can also be provided by addition to thereaction mixture of 1-azoniaspiroalkyl compounds. 1-Azoniaspiro [4.4]nonane is especially preferred. The organic templating component canalso be 1-azoniabicyclo [2.2.2] octane lower alkyl compounds, especiallysources of 1-azoniabicyclo [2.2.2] octane ethyl halides. The organicspecies can also be 2,2-methyl lower alkyl trimethylammonium compoundssuch as 2,2-dimethyl propyl trimethylammonium compounds.

The reaction mixture may be prepared using standard techniques. Typicalsources of aluminum oxide for the reaction mixture include aluminates,alumina, and aluminum compounds such as AlCl₃ and Al₂ (SO₄)₃. Typicalsources of silicon oxide include silicates, silica hydrogel, silicicacid, colloidal silica, tetraalkyl orthosilicates, and silicahydroxides. Gallium and germanium can be added in forms corresponding totheir aluminum and silicon counterparts. Salts, including alkali metalhalides such as sodium chloride, can be added to the reaction mixture.

The reaction mixture is maintained at an elevated temperature until thecrystals of the zeolite are formed. The reaction mixture temperatureduring hydrothermal crystallization is typically in the range from about110° C. to about 200° C., preferably from about 130° C. to about 180°C., and most preferably from about 135° C. to about 165° C. Thecrystallization period is typically greater than 1 day and preferablyfrom about 3 days to about 50 days.

The hydrothermal crystallization is usually conducted under pressure.Crystallization is usually carried out in an autoclave in which thereaction mixture is subject to autognous pressure. The reaction mixturecan be stirred during crystallization.

Once the zeolite crystals have formed, the solid product is separatedfrom the reaction mixture by any useful mechanical separation technique,such as filtration. The crystals should usually be washed with water anddried (e.g., at 90° C. to 150° C. for from 8 to 24 hours, usually atatmospheric or subatmospheric pressure) to provide the as-synthesizedSSZ-19 zeolite crystals.

During crystallization, the SSZ-19 crystals can be allowed to nucleatespontaneously from the reaction mixture. The reaction mixture can alsobe seeded with SSZ-19 crystals to direct and accelerate thecrystallization and minimize the formation of aluminosilicatecontaminants. If the reaction mixture is seeded with SSZ-19 crystals,the concentration of the organic templating agent can be greatlyreduced, but it is preferred to include some templating agent in thereaction mixture.

SSZ-19 can be used as synthesized or can be thermally treated(calcined). Calcination involves heating in air or otheroxygen-containing gas at a temperature of about 300° C. to about 820° C.or more, preferably from about 450° C. to about 700° C. The zeolite canbe leached with chelating agents (e.g., EDTA) or with dilute acidsolutions to increase the silica:alumina mole ratio. The zeolite canalso be steamed. Steaming can help to stabilize the crystalline latticeagainst attack from acids. For catalytic use, it is usually desirable toreplace the original alkali metal cation with hydrogen, ammonium, or aless basic metal ion. Typical metal cations for replacing sodium byion-exchange into the SSZ-19 crystal structure include, e.g., rareearth, Group IIA and Group VIII metals, as well as their mixtures.Cations of the rare earths, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al,Sn, Fe and Co are particularly preferred. SSZ-19 can also be compositedwith metals by impregnation or be otherwise intimately admixed with thezeolite using standard methods. Metals can be occluded in the crystallattice by having the desired metals present as ions in the reactionmixture from which the SSZ-19 is prepared. Especially useful metals forcombination with SSZ-19 include platinum, palladium, cobalt, nickel,molybdenum, tungsten, chromium, zinc, cadmium, manganese, vanadium andrhenium.

Conventional ion-exchange techniques can be used to introduce metals byion exchange. Normally the SSZ-19 is contacted with an aqueous solutionof the desired replacing cation or cations. Although a wide variety ofsalts can be employed, halides, especially chlorides, nitrates, andsulfates are particularly preferred. Ion exchange can be carried outeither before or after the zeolite is calcined. Following contact with asalt solution of the desired replacing cation, the zeolite is typicallywashed with water and dried at a temperature in the range of from 65° C.to about 315° C. After washing and drying, the zeolite can be calcinedin air or inert gas at a temperature in the range of from about 200° C.to 820° C. for a period of time ranging from 1 to 48 hours, or more, toproduce an active product especially useful in adsorption and catalysis.The exchange of cations has little, if any, effect on the zeolitelattice structures.

Depending on the desired use, SSZ-19 crystals can be provided in theform of a powder, granules, or shaped particles. In cases where thematerial is shaped, e.g., by pelleting or extrusion, it may be shapedbefore drying or may be dried or partially dried and then shaped.

The SSZ-19 crystals can be composited with other materials, particularlyrefractory inorganic oxides which are resistant to the temperatures andother conditions employed in dessication, adsorption and catalysis. Suchmaterials are useful for providing a matrix or binder for SSZ-19crystals. The binder may be active or inactive for adsorption orcatalysis. Suitable materials may include other synthetic or naturallyoccurring molecular sieves, but are usually amorphous refractoryinorganic materials such as naturally occurring and synthetic clays,silica and alumina. Alumina is a preferred binder. Suitablenoncrystalline inorganic oxides may be naturally occurring or may besynthesized in the form of gelatinous precipitates, sols, or gels,including mixtures of silica and metal oxides.

Use of known catalytically active materials in combination with SSZ-19in a catalyst can improve the overall properties of the catalyst.Catalytically inactive matrix of binder materials can serve as diluentsto control the rate of catalytic conversion.

In addition to single component synthetic binders such as silica,alumina, titania, and magnesia, SSZ-19 can be composited withmulti-component binders such as silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia, silica-titania,titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia,silica-alumina-magnesia and silica-magnesia-zirconia. A matrix can beprovided in the form of a gel or cogel.

Other natural and synthetic zeolites with which SSZ-19 may be compositedinclude, for example, faujasites (e.g., X and Y), erionites, mordenites,and ZSM-5. The combination of zeolites can also be composited with theporous inorganic matrix materials discussed above.

SSZ-19 is useful, for example, in catalysis and adsorption operations.SSZ-19 may be employed in hydrocarbon conversion processes in whichcarbon-containing compounds are changed to different carbon-containingcompounds. Examples of hydrocarbon conversion processes includecatalytic cracking, hydrocracking, and olefin and aromatics formation,isomerization of alkylaromatics, n-paraffins and naphthenes,oligomerization and polymerization of olefinically unsaturated compoundssuch as isobutylene and butene-1, naphtha reforming, aromatics andisoparaffins alkylation, and disproportionation of alkyl-aromatics, suchas forming benzene and xylenes, and higher methylbenzenes from toluene.

SSZ-19 can be used in conversion of hydrocarbonaceous feedstocks derivedfrom many different sources such as petroleum, shale oil, liquefied coaland tar sand bitumen. Depending on prior processing and the type ofprocessing to be carried out, the feed may contain metals, nitrogenand/or sulfur, or be free of metals, nitrogen and/or sulfur. In general,processing with SSZ-19 is more efficient (and the catalyst more active)when the metal, nitrogen, and sulfur contents of the feedstock are low.

Processes for conversion of hydrocarbonaceous feeds can be carried outin any conventional manner, e.g., fluidized bed, moving bed, or fixedbed operations.

Using catalysts containing an SSZ-19 component and a hydrogenationcomponent, heavy petroleum residual stocks, cycle stocks, and otherhydrocrackable charge stocks can be hydrocracked at hydrocrackingconditions including a temperature in the range of from 175° C. to 485°C., molar ratios of hydrogen to hydrocarbon charge from 1 to 100, apressure in the range of from 0.5 to 350 bar, and a liquid hourly spacevelocity (LHSV) in the range of from 0.1 to 30. For these purposes, theSSZ-19 catalyst can be composited with mixtures of inorganic oxidesupports as well as with faujasites such as X and Y.

SSZ-19 can also be used for naphtha reforming at reforming conditionsincluding a temperature in the range of from 315° C. to 595° C., apressure in the range of from 30 to 100 bar, and an LHSV in the range offrom 0.1 to 20. The naphtha reforming may be carried out at a hydrogento hydrocarbon mole ratio in the range of from 1 to 20.

SSZ-19 can be used to hydroisomerize normal paraffins when provided witha hydrogenation component, e.g., platinum. Hydroisomerization conditionsinclude a temperature in the range of from 90° C. to 370° C., and LHSVin the range of from 0.01 to 5, and a hydrogen to hydrocarbon mole ratioin the range of from about 1:1 to about 5:1, SSZ-19 can also be used toisomerize and polymerize olefins.

Other processes which can be carried out using catalysts containingSSZ-19 and hydrogenation metals such as platinum, include hydrogenation,dehydrogenation, denitrogenation, and desulfurization reactions.

SSZ-19 is particularly useful as an absorbent or adsorbent and dessicantfor, e.g., removing water from gas streams. It can also be used as afiller in paint and paper products, and a water-softening agent indetergents. Suitable absorption conditions for use with SSZ-19 include atemperature of 0° C. to 300° C. and a pressure of atmospheric or higher.

The following examples illustrate the preparation and use of SSZ-19.

EXAMPLES EXAMPLE 1 Preparation of N,N,N-Trimethyl Cyclopentyl AmmoniumIodide

250 Grams of cyclopentyl amine (Aldrich Chem.), 1090 grams oftributylamine (Aldrich Chem.), and 2.5 liters of N,N-dimethylformamidewere mixed in a 5-liter, round-bottom flask with stirring and cooling inan ice bath. 1251 Grams of methyl iodide were added dropwise to thecooled solution which was stirred overnight and allowed to come to roomtemperature. The crystals were collected by filtration and washed withacetone. More crystals were recovered by adding diethyl ether untilimmiscible phases formed, then adding just enough acetone to return toone phase, then chilling. The product obtained, N,N,N-trimethylcyclopentyl ammonium iodide, was correct according to microanalysis.

EXAMPLE 2 Preparation of 1-Azoniaspiro [4.4] Nonyl Bromide

The procedure used was basically that of Blicker et al. JACS, 76, 5099(1954), incorporated herein by specific reference, with a fewmodifications as noted. 40.8 grams (0.189 moles) of 1,4-dibromobutane(Aldrich), 7.56 grams of solid NaOH (0.189 moles) and 189 ml H₂ O wererefluxed. Over 1/2 hour, 13.4 grams of pyrrolidone (Aldrich) were addeddropwise to the refluxing mixture. Refluxing continued for another 1/2hour. The mixture was cooled in an ice/salt bath (ca. -10° C.) whilestirring. 94.5 Ml of cold 40% NaOH solution were added and an oilprecipitated. The oil was extracted into chloroform; the aqueous phasewas concentrated and more oil extracted into chloroform. After dryingwith MgSO₄, the chloroform was removed and the oil was crystallized inthe cold from a mixed solvent system of acetonitrile andtetrahydrofuran. The product salt was filtered rapdily under a cover ofether as the compound is hygroscopic. Microanalysis was correct for thedesired product.

EXAMPLE 3 Preparation of N-Ethyl Quinuclidinium Iodide

20 grams of Quinuclidine (1 Aza bicyclo [2.2.2] octane, Aldrich) weredissolved in 100 ml of chloroform with stirring and cooling in an icebath. 28.08 Grams of ethyl iodide (Aldrich) were added dropwise. Themixture became cloudy and was stirred overnight, slowly coming to roomtemperature. Acetone was added to the solution and then, with stirring,diethyl ether was added dropwise until crystals formed. The filteredsolids were washed with acetone and dried under vacuum. The product hadthe correct microanalysis for C, H, and N.

EXAMPLE 4 Preparation of N,N,N-Trimethyl Neopentylammonium Iodide

11.51 Grams of neopentylamine (Aldrich), 48.7 grams of tributyl amineand 100 ml of DMF were mixed and cooled. 56 Grams of methyl iodide(Aldrich) were added dropwise and the reaction as carried out and workedup as in Example 1.

EXAMPLE 5 Synthesis of SSZ-19 Using Template From Example 3

2.31 Grams of the template in Example 3, 5 grams of sodium silicatesolution (Banco "N" silicate, Na₂ O=9.08%, SiO₂ =29.22%), and 6 grams ofH₂ O were mixed in a teflon cup for a Parr 4545 reactor. A secondsolution of 0.50 grams of Al₂ (SO₄)₃. 18 H₂ O, 0.85 grams ofconcentrated NaOH solution, and 6 ml of H₂ O was added with stirring.The reactor was sealed and heated at 150° C. for 6 days with reactorstirring at about 30 rpm. Upon cooling to room temperature, the productwas filtered and washed with H₂ O five times. Air drying produced apowder whose X-ray diffraction pattern is that shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                              Relative                                                2 θ      d/n    Intensity                                               ______________________________________                                        7.88           11.22  11                                                      8.72           10.14  3                                                       11.72          7.55   25                                                      13.68          6.47   15                                                      15.84          5.59   13                                                      16.26          5.45   4                                                       17.41          5.09   3                                                       18.00          4.93   46                                                      18.40          4.82   2                                                       19.18          4.63   24                                                      20.92          4.25   8                                                       22.68          3.92   61                                                      23.76          3.74   32                                                      26.08          3.42   12                                                      27.42          3.25   42                                                      28.66          3.11   1                                                       30.00          2.98   8                                                       30.74          2.91   12                                                      ______________________________________                                    

EXAMPLE 6

5.09 Grams of "N" silicate solution were mixed with 12 ml of 0.8 molarsolution of the template of Example 1 in its hydroxide form (obtained byion exchanging the salt in Example 1 on Bio-Rad ion-exchange resinAG1-X8, concentrating the eluent, and titrating the concentrate todetermine molarity). 0.50 Grams of Al₂ (SO₄)₃. 18H₂ O were added anddissolved with mixing. the synthesis was carried out at the conditionsdescribed in Example 5. The SiO₂ :Al₂ O₃ mole ratio of the product, asdetermined by electron microprobe, was found to be 12:1. The X-raydiffraction pattern of the product is that of SSZ-19 as shown in Table3.

                  TABLE 3                                                         ______________________________________                                                              Relative                                                2 θ      d/n    Intensity                                               ______________________________________                                        5.56           16.04  1                                                       7.86           11.25  9                                                       8.65           10.22  2                                                       9.70           9.12   5                                                       11.30          7.83   6                                                       11.64          7.60   16                                                      12.90          6.86   2                                                       13.64          6.49   18                                                      14.85          5.97   3                                                       15.76          5.62   4                                                       16.15          5.49   2                                                       17.98          4.93   30*                                                     18.94          4.69   6                                                       19.06          4.66   10                                                      19.58          4.53    3*                                                     20.90          4.25   4                                                       22.62          3.93   40                                                      23.40          3.80   8                                                       23.74          3.75   29                                                      24.05          3.70   4                                                       24.57          3.62   2                                                       25.32          3.52   4                                                       26.00          3.43   1                                                       27.34          3.26   27*                                                     28.26          3.16   3                                                       28.94          3.09   1                                                       29.35          3.04   2                                                       29.94          2.98   5                                                       30.65          2.92   7                                                       ______________________________________                                         *Line is broad as a result of overlapping of two lines.                  

EXAMPLES 7-10

These are preparations of SSZ-19 carried out as described in Example 5and as shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Example:     7       8        9      10                                       ______________________________________                                        First Solution                                                                Sodium Silicate (g)                                                                        5 gm    5 gm     5 gm   5 gm                                     Template     Ex. 2   Ex. 4    Ex. 3  Ex. 1                                    Quantity (g) 1.77    2.21     6.90   5                                        H.sub.2 O (ml)                                                                             6       6        18     6                                        Second Solution                                                               H.sub.2 O (ml)                                                                             6       6        18     6                                        Al.sub.2 (SO.sub.4).sub.3                                                                  0.50    0.50     1.50   0.50                                     Conc. NaOH (g)                                                                             0.85    0.85     2.55   0.85                                     Time (days)  6       6        6      6                                        Temp. (°C.)                                                                         150     150      150    150                                      Stirring rpm 30      30       30     30                                       XRD          SSZ-19  50%      SSZ-19 SSZ-19                                                        SSZ-19   +      +                                                             50%      analcite                                                                             analcite                                                      analcite                                                 ______________________________________                                    

EXAMPLE 11

The hydrogen form of SSZ-19 was prepared from the SSZ-19 materialdescribed in Example 5. The Example 5 material was calcined in N₂ /lowair. The temperature was increased to 538° C. in 111° C. incrementsevery 2 hours, and held at 538° C. for 8-10 hours. The calcined materialwas ion exchanged four times with aqueous NH₄ NO₃ (2 hours at reflux foreach exchange) and then calcined again as above to give H⁺ -SSZ-19. TheX-ray diffraction lines are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                              Relative                                                2 θ      d/n    Intensity                                               ______________________________________                                        7.90           11.19  12                                                      8.78           10.07  1                                                       11.76          7.52   36                                                      13.64          6.49   39                                                      15.92          5.57   11                                                      17.55          5.05   2                                                       18.04          4.92   24                                                      18.44          4.81   1                                                       19.25          4.61   20                                                      20.89          4.25   5                                                       22.70          3.92   54                                                      23.72          3.75   22                                                      24.50          3.63   1                                                       26.18          3.40   8                                                       27.50          3.24   33*                                                     28.62          3.12   1                                                       29.98          2.98   10                                                      30.89          2.89   8                                                       ______________________________________                                         *Line is broad as a result of overlapping of two lines.                  

Using a Micromiretics Digisorb for analysis of N₂ absorption by the BETmethod, the surface area of the H-SSZ-19 of Example 11 was found to be259 m² /gm.

EXAMPLE 12

Absorption studies were carried out on the product of Example 11. Asample was left overnight at about 24° C. exposed to the ambientatmosphere at sea level. H₂ O absorption was 11.5% by weight after 24hours. Another sample was tested for n-hexane absorption, in a PerkinsElmer TGS-2 Thermogravimetric System. The sample was evacuated andheated at 300° C. to 375° C. for 1-2 hours. It was then cooled to roomtemperature in a vacuum. The sample was subjected to increasing n-hexanevapor pressures (vacuum liquid equilibrium) from 0° C. to 24° C. After48 hours, no n-hexane absorption was observed.

EXAMPLE 13

A sample of the catalyst of Example 11 was heated in a microreactorunder helium to 425° C. A feed of n-hexane and 3-methylpentane (50% eachby weight) was then passed in contact with the catalyst at 425° C. at anLHSV of 3 (based on ml of feed per gram of catalyst per hour). Theconversion to lower boiling hydrocarbons was 1-2%.

What is claimed is:
 1. A composition of matter comprising a crystallinesolid having a mole ratio of an oxide selected from silicon oxide,germanium oxide and mixtures thereof to an oxide selected from aluminumoxide, gallium oxide, and mixtures thereof greater than about 6:1, andhaving the X-ray diffraction lines of Table
 1. 2. A composition asdefined in claim 1 comprising, as synthesized and in the anhydrousstate, in terms of mole ratios of oxides as follows: (0.5 to 1.0)R₂ O:(0to 0.50)M₂ O:W₂ O₃ :(greater than 6) YO₂ wherein M is an alkali metalcation, W is selected from aluminum, gallium and mixtures thereof, Y isselected from silicon, germanium and mixtures thereof, R is an organicnitrogen or phosphorus cation.
 3. A composition as defined in claim 2wherein W is aluminum and Y is silicon.
 4. A composition of matterprepared by thermally treating the composition defined in claim 3, at atemperature from about 300° C. to 820° C.
 5. A composition as defined inclaim 1 wherein said mole ratio is above about 9:1.
 6. A composition asdefined in claim 1 which has undergone ion exchange with hydrogen,ammonium, rare earth metal, Group IIA metal, or Group VIII metal ions.7. A composition as defined in claim 1 wherein rare earth metals, GroupIIA metals, or Group VIII metals are occluded within the crystalstructure of said composition during synthesis.
 8. A composition ofmatter comprising the composition defined in claim 1 and an inorganicmatrix.
 9. A method for preparing the composition of claim 1,comprising:(a) preparing an aqueous mixture containing sources of anorganonitrogen compound, an oxide selected from aluminum oxide, galliumoxide, and mixtures thereof, and an oxide selected from silicon oxide,germanium oxide, and mixtures thereof, the aqueous mixture having thefollowing composition in terms of mole ratio of oxides:

    ______________________________________                                               YO.sub.2 /W.sub.2 O.sub.3                                                                    >6                                                             R.sub.2 O/W.sub.2 O.sub.3                                                                    0.5-40                                                  ______________________________________                                    

wherein R is an organonitrogen cation selected from the group consistingof cyclopentyltrimethylammonium cations, 2,2-dimethylpropyltrimethylammonium cations, ethyl-1-azoniabicyclo [2.2.2.] octanecations, 1-azoniaspiro [4.4] nonane cations, or mixtures thereof, Y issilicon, germanium or mixtures thereof, W is aluminum, gallium ormixtures thereof, wherein said aqueous mixture has a mole ratio of OH⁻/YO₂ of 0.95 to 1:1 and (b) maintaining the mixture at a temperature ofat least 100° C. until crystals of said composition form.
 10. A methodin accordance with claim 9 wherein the aqueous mixture has a compositionin terms of mole ratios of oxides falling in the ranges: YO₂ /W₂ O₃, 3:1to 350:1; R₂ O/W₂ O₃, 0.5:1 to 40:1; wherein Y is selected from silicon,germanium and mixtures thereof, W is selected from aluminum, gallium,and mixtures thereof, and R is an organonitrogen cation selected fromthe group consisting of cyclopentyltrimethylammonium cations,2,2-dimethylpropyl trimethylammonium cations, ethyl-1-azoniabicyclo[2.2.2] octane cations, 1-azoniaspiro [4.4] nonane cations, or mixturesof them.